AU4518199A

AU4518199A - Exhaust gas catalyst comprising rhodium, zirconia and rare earth oxide

Info

Publication number: AU4518199A
Application number: AU45181/99A
Authority: AU
Inventors: Paul Joseph Andersen
Original assignee: Johnson Matthey PLC
Current assignee: Johnson Matthey PLC
Priority date: 1998-06-22
Filing date: 1999-06-16
Publication date: 2000-01-10
Anticipated expiration: 2019-06-16
Also published as: MXPA00012923A; JP4454855B2; NO20006550D0; AU737460B2; BR9911494A; NZ509109A; DE69910791T2; CZ297085B6; MX220384B; JP2002518171A; WO1999067020A1; CA2335812A1; ES2207236T3; CN1313787A; US6692712B1; IN2001MU00029A; EP1098702A1; KR100604139B1; KR20010053142A; CA2335812C

Description

WO 99/67020 PCT/GB99/01914 EXHAUST GAS CATALYST COMPRISING RHODIUM, ZIRCONIA AND RARE EARTH OXIDE This invention relates to a catalyst and a method of catalysing a chemical reaction employing it. 5 Rhodium is often used as a catalytically active material, paticularly for reducing nitrogen oxides (NOx) to nitrogen. It is used as a catalytically active component of a three way catalyst (TWC) which combats air pollution from engine exhaust gas by converting NOx to nitrogen, CO to CO 2 and hydrocarbons (HC) to CO 2 and H 2 0. TWC's achieve high 10 conversions of CO and NOx by containing as catalytically active material a large amount of palladium, for instance 1OOg per ft 3 (per 0.028m 3 ), or a combination of a small amount of rhodium, for instance 6g per ft 3 (per 0.028m 3 ), with a moderate amount of palladium, for instance 54g per ft 3 (per 0.028m 3 ), or with a moderate amount of platinum, for instance 33g per ft 3 (per 0.028m 3 ), or with moderate amounts of palladium and platinum. The precious 15 metal components platinum, palladium and rhodium, however, are rare and expensive, and can account for a large proportion of the total cost of a catalyst. It would be desirable, therefore, to discover a new catalyst which achieves high activity from a lower content of these precious metal components. The catalyst should meet the exacting conditions to which it is subjected in use, for instance being of high thermal stability. In addition, TWC's 20 containing large amounts of palladium have been found to be particularly sensitive to poisoning by sulphur species emanating from the engine fuel, and it would be desirable to reduce or avoid that poisoning. The present invention provides such an improved catalyst. Accordingly, the invention provides a catalyst comprising rhodium on a support, the 25 support comprising: (a) 52-95% zirconia, and (b) 5-48% rare earth oxide, based on the total weight of (a) and (b), the concentration of the rhodium on the support being 0.035-0.35% based on the total weight of the rhodium and the support, and the catalyst 30 containing 1.2-4.0g per in 3 (g per 16.4cm 3 ) in total of (a) and (b).

WO 99/67020 PCT/GB99/01914 2 The invention also provides a method of catalysing a chemical reaction comprising the reduction of nitrogen oxide to nitrogen, which method comprises contacting the nitrogen oxide with the catalyst. 5 There is much prior art on catalysts, but none has disclosed the present catalyst. US specification 5057483 discloses a catalyst composition comprising a carrier on which is disposed a catalytic material, the catalytic material comprising: a first coat carried on the carrier and comprising a first activated alumina support, a 10 catalytically effective amount of a first platinum catalytic component dispersed on the first alumina support, and a catalytically effective amount of bulk ceria; and a second coat carried by the carrier and comprising a co-formed rare earth oxide-zirconia support, a catalytically effective amount of a first rhodium catalytic component dispersed on the co-formed rare earth oxide-zirconia support, a second activated alumina support, and 15 a catalytically effective amount of a second platinum catalytic component dispersed on the second alumina support. PCT specification WO 98/03251 discloses a method of making a platinum group metal three-way catalyst composition which contains a high temperature catalytic component 20 and a low temperature catalytic component with each catalytic component being present in the catalyst composition as separate distinct particles in the same washcoat layer which method comprises: (a) forming on a non-porous substrate a combined washcoat of a high temperature catalyst support material and a low temperature catalyst support material from a slurry in 25 which each of the catalyst support materials is of sufficiently large particle size so as to prevent each catalyst support material from forming a solution or a sol with the liquid medium of the slurry; and (b) impregnating a platinum group metal or metals into each catalyst support material either after formation of the washcoat on the non-porous substrate or before forming the 30 washcoat slurry.

WO 99/67020 PCT/GB99/01914 3 The present catalyst is of surprisingly high activity, especially for the reduction of nitrogen oxide to nitrogen, particularly in combination with the oxidation of CO to CO 2 . It also is of high activity for the oxidation of HC to CO 2 and H20. It has high thermal durability. Thus, it is particularly effective as a TWC. It does not require the presence of 5 Pt or Pd. The present catalyst contains only a low concentration of Rh on the support, but omitting Pt and Pd from prior art catalysts and including only this low concentration of Rh results in relatively low NOx conversion and low CO and IC conversions. The present catalyst can provide the same conversion of CO to CO 2 and of NOx to nitrogen as prior art catalysts containing the same amount of Rh but in addition Pd. The present catalyst is less 10 sensitive to S poisoning than are catalysts based primarily on Pd at high loading. The present catalyst comprises a low concentration of rhodium on a particular support whose essential components are present in high concentration in the catalyst. 15 The catalyst can be in conventional form, for instance a pellet bed or foam but preferably a honeycomb monolith through whose holes engine exhaust gas flows and in whose holes the rhodium on a support is carried. The catalyst, whether it be a monolith or pellet bed or foam or otherwise will have a certain overall volume, and it is to this volume that the 1.2-4.Og per in 3 (per 16.4cm 3 ) concentration of the zirconia and rare earth oxide of 20 the zirconia plus rare earth oxide support relates. The volume includes the voids within the catalyst, for instance the unoccupied parts of a monolith through which the gas flows; this is a convenient way of expressing the concentration. The catalyst contains 1.2-4.0g, preferably 1.2-3.2g, per in 3 (per 16.4cm 3 ) in total of 25 the zirconia and rare earth oxide of the zirconia plus rare earth oxide support. The concentration of rhodium on the support is 0.035-0.35%, preferably 0.1-0.35%, based on the total weight of the rhodium and the support. The present support comprises (a) 52-95% zirconia and (b) 5-48% rare earth oxide, 30 preferably (a) 52-88% zirconia and (b) 12-48% rare earth oxide, especially (a) 72-82% zirconia and (b) 18-28% rare earth oxide, based on the total weight of (a) and (b). The rare earth oxide is preferably one or more of cerium oxide, lanthanum oxide, neodymium oxide, WO 99/67020 PCT/GB99/01914 4 praseodymium oxide and yttrium oxide. Preferably, the rare earth oxide comprises ceria. Advantageously, the rare earth oxide is ceria together with other rare earth oxide. Preferably, the support comprises: (a) 52-88% zirconia, 5 (b') 10-40% ceria, and (b") 2-8% rare earth oxide other than ceria, based on the total weight of (a), (b') and (b"). The support comprises especially: (a) 72-82% zirconia, (b') 15-25% ceria, and 10 (b") 3-5% rare earth oxide other than ceria, based on the total weight of (a), (b') and (b"). (a) and (b) preferably constitute 100% of the support though other materials can also be present; alumina, however, is preferably avoided, so as to avoid rhodium-alumina 15 interactions. Usually, (a) and (b) constitute 90-100% by weight of the support. Especially preferred is the support consisting essentially of (a) 72-82% zirconia, (b') 15-25% ceria, and (b") 3-5% rare earth oxide other than ceria, 20 based on the total weight of (a), (b') and (b"). The rare earth oxide other than ceria is usually one or more of lanthanum oxide, neodymium oxide, praseodymium oxide and yttrium oxide. Preferably the rare earth oxide other than ceria comprises lanthanum oxide. 25 The catalyst comprises rhodium on the support. It can contain additional materials, which can be conventional in themselves. For instance, the rhodium on the support can be in admixture with H 2 S suppressant material, eg one or more of NiO, Fe 2 0 3 , Co 3 0 4 and MnO 2 ; NiO is preferred. Alternatively, the H 2 S suppressant material can be in a layer over 30 the rhodium on the support. The loading of the H 2 S suppressant material is usually 0.05-0.5g per in3 (per 16.4cm 3

).

WO 99/67020 PCT/GB99/01914 5 The rhodium on the support can be in admixture with material to improve adhesion of a washcoat layer containing the rhodium on the support, for instance adhesion to a monolith, or with material to stabilise the washcoat layer against sintering at high temperatures. A preferred material which performs both functions is particulate oxide which 5 is a mixture of alumina and lanthanum oxide, preferably containing 2-7% lanthanum oxide based on the total weight of the alumina and lanthanum oxide. The rhodium on the support can be in admixture with other catalytically active material, particularly comprising one or more of Rh, Pt and Pd, on a separate support. 10 Preferably, however, no other Rh is present. By having Pt and/or Pd on this separate support they are distinct from the Rh on the present support. The separate support can be a conventional oxide support. Alternatively, the other catalytically active material on a support can be in a separate layer from the rhodium on the support. 15 The rhodium which is on the support comprising (a) and (b) can be in admixture with other catalytically active material, especially Pt and/or Pd, on that support. It is preferred, however, that the rhodium on the support is free from Pt and Pd; it is preferred to keep any Pt and/or Pd distinct. 20 The catalyst usually contains 1-25g, for instance 1-9g, per ft 3 (per 0.028m 3 ) of the rhodium which is on the support comprising (a) and (b). The catalyst can contain promoters. When it contains Pd, base metal promoters such as alkaline earth, for instance Ba, promoters or La or Nd promoters, can be present. 25 The catalyst can be prepared in any appropriate way, for instance a way which is conventional in itself. Rh precursor is preferably deposited on the support comprising (a) and (b), and the support bearing the Rh precursor calcined. Before or after forming the support bearing the Rh, the support is preferably coated onto a carrier such as a honeycomb 30 monolith. The coating can be done by dipping the monolith into an aqueous slurry of the support or by passing the monolith through a curtain of the slurry. The slurry can contain additional materials, or precursors thereof, which the catalyst is to contain, such as the WO 99/67020 PCT/GB99/01914 6 materials discussed above. Alternatively or additionally, additional materials, or precursors thereof, can be introduced in a layer above or below the layer comprising the rhodium on the support, but this is not preferred. The layer above or below can be introduced in an analogous way to that in which the rhodium on the support is introduced, usually by means 5 of an aqueous slurry. The Rh precursor can be deposited on the support by impregnating an aqueous solution of Rh precursor, such as RhCl 3 or preferably Rh(NO ) 3 igto the support. Alternatively, Rh precursor can be deposited on the support by precipitation, for instance by 10 hydrolysis of a Rh salt such as Rh(NO 3

)

3 . Preferably, an aqueous solution of Rh precursor is impregnated into the support, the impregnated support is formed into an aqueous slurry, the aqueous slurry is coated on the carrier, and the coated carrier calcined. The Rh precursor which is deposited on the support can be in admixture with other 15 materials (or precursors thereof, eg Pt and/or Pd precursors) which are to be present in the same layer as the Rh. Alternatively such other materials or precursors can be deposited on the support separately, for instance after coating the support onto the carrier. The catalyst is useful for catalysing a chemical reaction comprising the reduction of 20 nitrogen oxide to nitrogen, by contacting the nitrogen oxide with the catalyst. The catalyst is especially useful for combatting air pollution from engine exhaust gas containing nitrogen oxide, carbon monoxide and hydrocarbon, by contacting the exhaust gas with the catalyst. The catalyst can be used in ways which are conventional in themselves. The engine is preferably that of a vehicle, especially a car. The engine is preferably a petrol (gasoline) 25 engine. The catalyst can be positioned close-coupled to the engine or preferably under the floor of the vehicle. The catalyst can be employed with other catalysts, for instance it can be employed as an under-floor catalyst in conjunction with a close-coupled catalyst. The invention is illustrated by the following Examples. 30 WO 99/67020 PCT/GB99/01914 7 EXAMPLE 1 A CeLa-stabilised zirconia/Rh material was prepared by impregnating an aqueous 5 solution of Rh(N0 3

)

3 into a CeLa-stabilised zirconia material by the incipient wetness technique to a concentration of 0.22% Rh by weight. The incipient wetness technique is a known technique, in which a sample of the material to be impregnated is contacted with increasing volumes of water until no more is absorbed so as to determine the maximum volume which the material will hold and then material to be impregnated is contacted with 10 this volume of aqueous solution of impregnant. The CeLa-stabilised zirconia material had a composition of 4% La 2 0 3 , 20% CeO 2 and 76% ZrO 2 . Bulk NiO was slurried in water at a composition of about 4% by weight solids and wet milled to a mean particle size of about 6 microns. After the NiO slurry had been wet milled, the CeLa-stabilised zirconia/Rh was added to it and the resulting slurry was wet milled further to a mean particle size of about 15 5 microns to form slurry (A) with a solids composition of about 65% by weight. Separately, La-stabilised alumina of composition 4wt% La 2

O

3 and 96wt% Al 2 03 was slurried in water at a composition of about 40% by weight solids and then wet milled to a mean particle size of about 5 microns to form slurry (B). Slurry (A) and slurry (B) were blended in the weight ratio (A):(B) = 2.42:1 on a solids basis and adjusted to a solids composition of 20 approximately 50% by weight and coated on a conventional cordierite honeycomb monolith having 400 holes per square inch (per 6.45 square cm) by dipping. After blowing off the excess washcoat with compressed air, the coated substrate was then dried at 60'C and calcined at 500'C in flowing air. 25 The total loading was 2.39g per in 3 (per 16.4cm 3 ) with a composition by weight of 29.21% La-stabilised alumina, 66.87% CeLa-stabilised zirconia, 3.77% NiO and 0.15% Rh. Accordingly, the catalyst comprised rhodium on a support consisting of 76% zirconia, 20% ceria and 4% lanthanum oxide and contained 1.60g per in 3 (per 16.4cm 3 ) in total of the zirconia and rare earth oxide of the zirconia plus rare earth oxide support. 30 WO 99/67020 PCT/GB99/01914 8 COMPARATIVE EXAMPLE 1 Bulk NiO was slurried in water at a composition of about 4% by weight solids and wet milled to a mean particle size of about 6 microns. Zr-stabilised ceria was added to the 5 resulting NiO slurry which was then wet milled further to a mean particle size of about 5 microns to form slurry (A) with a solids composition of about 65% by weight. The Zr-stabilised ceria had a composition of 58% CeO 2 and 42% ZrO 2 . Separately, La-stabilised alumina of the same composition as that of Example 1 was slurried in water at a composition of about 40% by weight solids and then wet milled to a mean particle size of about 10 5 microns to form slurry (B). Slurry (A) and slurry (B) were blended in the weight ratio A:B = 2.42:1 on a solids basis and adjusted to a solids composition of approximately 50% by weight and coated on a monolith identical to that of Example 1 by dipping. After blowing off the excess washcoat with compressed air, the coated substrate was then dried at 60'C and calcined at 500 C in flowing air. The resulting coated substrate was 15 impregnated with Pd:Rh:Nd from a Pd(N0 3

)

2 :Rh(NO 3

)

3 :Nd(NO3) 3 solution which also contained 150g/litre citric acid, and then again dried at 60'C and calcined at 500'C in flowing air. The substrate was then impregnated with barium from a barium acetate solution, and yet again dried at 60'C and calcined at 500 C in flowing air. 20 The total loading was 3.05g per in 3 (per 16.4cm 3 ) with a composition by weight of 23.0% La-stabilised alumina, 52.5% Zr-stabilised ceria, 3.0% NiO, 7.0% Nd203, 13.4% BaO, and 0.99% Pd and 0.11% Rh. Accordingly, the catalyst comprised rhodium on a support consisting of 58% ceria and 42% zirconia, and contained 1.60g per in 3 (per 16.4cm 3 ) in total of the zirconia and rare earth oxide of the zirconia plus rare earth oxide support. 25 This catalyst is a commercially available TWC. COMPARATIVE EXAMPLE 2 Comparative Example 1 was repeated except that no Pd(N0 3

)

2 was employed, so 30 that the product contained no Pd.

WO 99/67020 PCT/GB99/01914 9 The total loading was 3.01g per in 3 (per 16.4cm 3 ) with a composition by weight of 23.19% La-stabilised alumina, 53.10% Zr-stabilised ceria, 2.99% NiO, 6.98% Nd 2 03 13.62% BaO and 0.12% Rh. Accordingly, the catalyst comprised rhodium on a support consisting of 58% ceria and 42% zirconia, and contained 1.60g per in 3 (per 16.4cm 3 ) of the 5 zirconia and rare earth oxide of the zirconia plus rare earth oxide support. EXAMPLE 2 AND COMPARATIVE EXAMPLES 3 AND 4 The catalysts described in Example 1 and Comparative Examples 1 and 2 were each 10 aged on an engine dynamometer cycle which simulates 100,000 miles of road ageing. The cycle had catalyst temperatures ranging from 850'C to 1000 0 C and a duration of 120 hours. After this ageing, the catalyst was fixed to a test engine dynamometer and the percent conversions of hydrocarbon (HC), carbon monoxide (CO) and nitrogen oxide (NOx) in the exhaust gas measured at various air/fuel ratios with an exhaust gas temperature at the 15 catalyst inlet of 450'C. At a particular air/fuel ratio (which is near the stoichiometric ratio), the CO and NOx percent conversions are equal and this conversion value is referred to as the CO/NOx cross-over point (COP). The COP for each catalyst after ageing is shown in Table 1 together with the HC efficiency at the same air/fuel ratio at which the COP occurs. The COP and HC efficiencies together represent the TWC activity. 20 TABLE 1 TWC Activity After 100,000 Miles Simulated Road Ageing Sweep Cross-over 25 Catalyst (% Conversion) HC CO/NOx Example 2 Example 1 81 89 Comparative Comparative Example 3 Example 1 89 87 Comparative Comparative 30 Example 4 Example 2 44 44 WO 99/67020 PCT/GB99/01914 10 Each of the catalysts contained substantially the same amount of Rh, but it can be seen from the Table that the catalyst of Example 1 had CO and NOx conversion activities which were equivalent to those of a standard TWC which contained in addition a significant quantity of the expensive precious metal Pd. It can also be seen that merely omitting Pd 5 from the standard TWC resulted in a drastic loss in activity. EXAMPLE 3 The procedure of Example 1 was followed except that the concentration of Rh in the 10 impregnated CeLa-stabilised zirconia was 0.11% by weight and the total loading was 4.70g per in 3 (per 16.4cm 3 ), the composition being by weight 68.09% CeLa-stabilised zirconia, 29.78% La-stabilised alumina, 1.92% NiO and 0.076% Rh. EXAMPLE 4 15 The catalyst of Example 3 was tested in the procedure described in Example 2, and gave the following results: TABLE 2 20 TWC Activity After 100,000 Miles Simulated Road Ageing Sweep Cross-over (% Conversion) HC CO/NOx 25 77 81 Within the standard deviations experienced in these tests, the results shown in Table 2 are equivalent to those shown for Example 2 in Table 1. 30

Claims

1. A catalyst comprising rhodium on a support, the support comprising: (a) 52-95% zirconia, and 5 (b) 5-48% rare earth oxide, based on the total weight of (a) and (b), the concentration of the rhodium on the support being 0.035-0.35% based on the total weight of the rhodium and the support, and the catalyst containing 1.2-4.Og per in 3 (g per 16.4cm 3 ) in total of (a) and (b). 10

2. A catalyst according to claim 1, wherein (a) and (b) constitute 90-100% by weight of the support.

3. A catalyst according to claim 1 or 2, wherein the support comprises (a) 52-88% zirconia, and 15 (b) 12-48% rare earth oxide, based on the total weight of (a) and (b).

4. A catalyst according to claim 1 or 2, wherein the support comprises: (a) 52-88% zirconia, 20 (b') 10-40% ceria, and (b") 2-8% rare earth oxide other than ceria, based on the total weight of (a), (b') and (b").

5. A catalyst according to claim 1, wherein the support consists essentially of: 25 (a) 72-82% zirconia, (b') 15-25% ceria, and (b") 3-5% rare earth oxide other than ceria, based on the total weight of (a), (b') and (b") 30

6. A catalyst according to claim 4 or 5, wherein the rare earth oxide other than ceria is lanthanum oxide. WO 99/67020 PCT/GB99/01914 12

7. A catalyst according to any one of the preceding claims which contains 1-25g per ft 3 (per 0.028m 3 ) of the rhodium.

8. A catalyst according to any one of the preceding claims, wherein the rhodium on the 5 support is free from platinum and palladium.

9. A catalyst according to any one of the preceding claims which is free from platinum and palladium.

10 10. A catalyst according to any one of the preceding claims, wherein the rhodium on the support is in admixture with H 2 S suppressant material.

11. A catalyst according to any one of the preceding claims, wherein the rhodium on the support is in admixture with particulate oxide which is a mixture of alumina and lanthanum 15 oxide.

12. A catalyst according to any one of the preceding claims which comprises a honeycomb monolith through whose holes engine exhaust gas flows and in whose holes the rhodium on a support is carried. 20

13. A method of catalysing a chemical reaction comprising the reduction of nitrogen oxide to nitrogen, which method comprises contacting the nitrogen oxide with a catalyst claimed in any one of the preceding claims. 25

14. A method of combatting air pollution from engine gas containing nitrogen oxide, carbon monoxide and hydrocarbon, which method comprises contacting the exhaust gas with a catalyst claimed in any one of claims 1-12.

15. A method according to claim 14, wherein the engine is that of a vehicle. 30

16. A method according to claim 14 or 15, wherein the engine is a petrol engine.